Siloxane azo dyestuffs



,alkoxy radicals, and the like.

2,927,839 SILOXANE AZO DYESTUEFS Donald L. Bailey, Snyder, and Ronald M. Pike, Grand Island, N.Y., assignors .toUnion Carbide Corporation, a corporation of New York No Drawing, Application April 29, 1957 se ial No. 655,507

12 Claims. ((31. s-'s Y This invention relates to silicon-containing azo dyestuffs and to processes for producing them. More particulariy, this invention is concerned with polysiloxane azo dyestuffs.

The siloxane azo dyestulfs of the present invfinlion contain units which can be represented by the following general formula:

[R--N '=N -Ar- C H Si 1 wherein R represents the residue of a coupling compo.- nent, as for example, substituted aryl radicals such as phenyl, naphthyl, anthraquinolyl or pyrazolyl radicals; Ar represents an arylene radical such as a phenylene radical and including a substituted phenylene radical; a

is an integer having a value of from 0 to about 8 'or higher and preferably from 0 to about 4;and c is an integer having a value of 05,-1.6 and 1.5. The ..sub-

States Patent 0 7 2,927,839 Patented Mar.

"hydrous organic medium (Procedure B), that is containdimethylfozmamide, and the like.

ing less than about 2% by Weight of water, produces a functional diazonium salt. Among the organic solvents 7 suitable for use are dioxane, acetic acid, ethylene glycol,

The arylaminoalkoxysilane is dissolved in the solvent, and dry hydrogen chloride gas isbubbled into the solution. The aminemay V then'be diazotized With'a solvent solution of sodium nitrite.- h

After the diazonium salt has been produced by either Procedure A or Procedure B, it is added to the coupling component and the dyestufl. is formed by the mam tion of diazonium salt and coupling component. 'This coupling reaction may be carried outin aqueous medium or under substantially anhydrous conditions. The .2120

- dyestuffs produced will be, polysiloxane azo dyestuffs stituents on the arylene radical: may bealkyl radicals,

which may be attached to the aryl radical, R, are halogen atoms, hydroxy, alkoxy, alkyl, sulfo, sulfonamide, unsub-w stituted arylazo, substituted. arylazo, phenyl, nitro, or acylamino radicals, and the like.

The novel siloxane azo dyestufis herein disclosed and claimed contain the unit represented by the following general formula:

2 wherein R, Ar and a have the samemeanings as hereinbefore indicated; Y represents an alkyl radical such as methyl, ethyl, propyl, and the like; and b is an integer having a value of from 0 to '2. V

The valuable polysiloxane dyestuffs of this invention are produced by diazotiz ing an anunoarylalkoxysilane represented by the general formula:

wherein Ar, Y and a have the same meanings 'as hereinbefore indicated; V represents an alko'xy radical such as methoxy, ethoxy, propoxy, and'the like; and

d is an integer having a value of from 1 to '3, and

coupling the produced diazoniurn salt with an aromatic coupling component. f

I The diazotization of the aminoarylalkoxysilane can be carried out in an anhydrous organic solvent medium Among the substituents Whenever the diazotization, or coupling, or both are carried out in the presence of water.

1-amino 4-(beta-triethoxysilylethyl -benzen e, l-amino-4-triethoxysilylbenzene, 1amino-4-diethoxymethylsilylhenzene, 1-amino-2-methyl-4- (beta-triethoxysilylpropyl -benzene, l-aininolgamma-ethoxydimethylsilylpropyl) benzene, l-amino-3-(beta-triethoxysilylethyl)-4-methoxybcnzene, l-amino 3-methyl-4- (beta-triethoxysilylethyl) -benzene, l-amino-4- (beta-diethoxymethylsilylethyl) -benzene, 1-amino-4-ethoxydimethylsilylbenzene, and the like.

The preparation of these aminoarylalkoxysilanes is the subject matter of ourc'opending patent application, Serial No. 655,506, filed April 29, 1957.

As coupling component one can use any aromatic compound capable of coupling. .Among the suitable cou I pling components are the phenols, the anilines, the naph thols, the naphthylamines, the pyrazolones, and the like. Depending on the coupling component selected, one can prepare the metal complex of the dyestulf ,usingihe salts of metals such as Cr, Co, Ni, Mn,- Fe, Cd and Sn by methods which are Well known in dye'stuif; technology. Illustrative of the aromatic coupling components suita ble in this invention are:

Aniline, Z-methylaniline, 3-methylaniline', 2,5-dimethylaniline, .Z-aminobenzene sulfonic acid,

3-aminobenzene sulfonic acid, f

or in an aqueous medium; In preparingthe diazonium.

salt in an aqueous mixture (Procedure A) 'theamiuo arylalkoxysilane is dissolved or suspended in a cold dilute "acid solution, as for example hydrochloric acid, and is then diazotized by method well known in dyestufi tech nology, for example by the addition of a sodium nitrite solution. When the diazonium salt is prepared in aqueous medium, the functional alkoxy radicalsundergo hydrolysis and a siloxane diazonium salt is obtained. The preparation of the diazonium salt in a substantially an- Z-methoxyaniline,

iZ-methoxy-S-methylaniline, 2,5-dimethoxyaniline,

2,5-diethoxyaniline, 2-chloro-S-methoxyaniline, 1,3-diaminobenzene, 2,4-diaminotoluene, 2,4-diaminobenzene sulfonic acid, N,N-dimethylaniline, N-methylaniline, V

' Phenol,

Phenol-surnames; Phen0l-4-sulfonic acid, 4-acetaminophenol,

4-tert. amylphenol,

3-methoxyphenol,

Z-methylphenol,

4-methylphenol,

1,3-dihydroxybenzene,

lshydroxybenzoic acid,

2-hydroxy-3-methylbenzoic acid,

Z-aminophenol,

S-aminophenol,

2-aminophenol-4-sulfonic acid 2-aminophenol-4-sulfonamide,

l-naphthol,

1-hydroxynaphthalene-4-sulfonic acid,

l-hydroxynaphthalene--sulfonic acid,

l-hydroxynaphthaleneB,-disulfonic acid,

l-hydroxyrraphthalene-4,S-disulfonic acid,

l,8-dihydroxynaphthalene-4-sulfouic acid,

1,8-dihydroxynaphthalene-3,6-disulfonic acid,

1,S-dihydroxynaphthalene-3,7-disulfonic acid,

Z-naphthol,

Z-hydroxynaphthalene-6-sulfonic acid,

2-hydroxynaphthalene-3,6-disulfonic acid,

Z-hydmxynaphthalene-6,8-disulfonic acid,

l-hydroxy--phenylaminonaphthalene-3-sulfonic acid,

l-hydroxy-8-acetaminonaphthalene-3,-disulfonic acid,

l-hydroxy-6-acetaminonaphthalene-4-sulfonic acid,

l-naphthylamine,

l-aminonaphthalene-4-sulfonic acid,

l-aminonaphthalene 6-sulfonic acid,

l-aminonaphthalene-3,6-disulfonic acid,

Z-naphthylamine,

2-aminonaphthalene-fi-sulfonic acid,

l-amino-8-hydroxynaphthalene-4-sulfonic acid,

2-amino-5-hydroxynaphthalene-7-sulfonic acid,

Z-amino-8-hydroxynaphthalene-6-sulfonic acid,

1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,

l-amino-8-hydroxynaphthalene-2,4-disulfonic acid,

Z-amino-8-hydroxynaphthalene-3,6-disulfonic acid,

Benzoylacetonitrile,

Acetoacetanilide,

l-phenyl-3-methyl-5-pyrazolone,

l-(3-chlorophenyl)-3-methyl-5-pyrazolone,

1-(4'-sulfophenyl)-3-methyl-5-pyrazolone,

1-(4' sult'ophenyl)-5-pyrazolone-3-carboxylic acid,

Copper complex of 3-(2', 4'-dihydroxyphenylazo) -4-hydroxybenzenesulfonic acid,

2-methoxy-4-chloroacetoacetanilide,

1- (2'-methyl-4-amino-5 '-methoxyphenylazo) -8-hydroxynaphthalene-3,6-disulfonic acid, and the like.

This enumeration is illustrative of the large number of compounds which can be used as coupling components, and is not to be considered as limitative. As hereinbe fore indicated, the coupling is performed by procedures well known in dyestufi technology. The polysiloxane azo dyestuffs are obtained as polymeric type materials. The shades of the azo dyestuffs obtained vary from yellows to oranges, reds, blues, greys and browns; and the color of the dyestutf produced will vary according to the paritficular components selected to produce the dyestu 7 When the aminoarylalkoxysilane selected as diazo component is a trifunctional alkoxy silane, the azo dyestuffs obtained contain the unit represented'by the general formula:

and when the aminoarylalkoxysilane is adifunctional alkoxy silane, the dyestuffs contain the unit represented by the general formula:

Y [RN=NAr o .111 ,S iO

wherein e has a value of at least 3 and may be as high as 7 for cyclic polysiloxanes and higher for linear polysiloxanes, while if the aminoarylalkoxysilane is monofunctional then the azo dyestufis are the disiloxanes having the general formula:

Ya [RN=NAro.Hi..-Si0i/zl The dyestuffs of this invention show some solubility in mixtures of water and organic solvents such as alcohol, acetone and dioxane, and in organic solvents such as alcohols, dimethylformamide and pyridine. The presence of solubilizing groups, such as sulfo or carboxy radicals in the R radical imparts some solubility in water alone. Dyeing can be carried out either from solution, or from suspension, at temperatures'above about 25 C., preferably at the boiling point of the dyebath.

If desired, the dyeing may be carried out from a dye bath consisting of the dyestufi dissolved in an organic solvent.

The polysiloxane azo dyestuils of this invention are substantive to natural fibers such as wool, silk and cotton, and also to synthetic fibers such as nylon, Dynel, viscose, acetate, and the like. In addition the poly siloxane dyestuifs of this invention are characterized by the very useful property of dyeing glass cloth and silica from an aqueous dyebath solution, not heretofore possi ble as far as is known. These dyeings have good wash fastness and other properties. It has also been found that these polysiloxane azo dyestufis impart some waterrepellency to the natural fibers dyed therewith. Satisfactory ink formulations can also be prepared.

The following examples further serve to illustrate the invention.

Example. 1

There was dissolved 1.55 g. of l-amino-4-(beta-triethoxysilylethyl) -benzene in a mixture of 3 ml. of water and 3 ml. of 20 B. hydrochloric acid. The mixture was cooled to 5 C. and diazotized in the usual manner with a solution of 0.38 g. of sodium nitrite in 5 ml. of water. The pale yellow diazo solution was coupled under ice cooling with a solution of 0.705 g. of 2-naphthol dissolved in 30 ml. of ethanol and containing 3 ml. of 20% by weight sodium hydroxide solution. A red dyestufi was obtained. The reaction mixture was stirred until coupling was completed and the precipitated dyestufi was isolated by filtration. Yield was 1.2 g. of the siloxane dyestuif represented by the following formula:

The NzSi ratio found by microanalysis was 2.0321 as compared to a theoretical value of 2.00:1.

Example 2 The polysiloxane azo dyestufi described in Example 1 was prepared using 4.65 g. of l-amino-4-(beta-triethoxysilylethyl)-benzene and 2.13 g. of Z-naphthol. The wet cake isolated from the coupling reaction was charged to a one liter three-necked flask containing a solution of 110 g. of sodium chloride in 500 ml. of water. The flask was equipped with a stirrer, thermometer, reflux condenser and heating mantle. The reaction mixture in the flask was heated with stirring to 70 to C. and a solu tion of 8 g. of copper sulfate decahydrate in 55 ml. of water and 52.5 ml. of concentrated aqueous ammonia was added. The whole was then stirred at 85 to C. overnight. The copper complex of the siloxane azo dyestufi so formed was .filtered and dried. It was a brown-red powder weighing 7.1 g., and was insoluble in diluterbase, but soluble. in dilute hydrochloric acid, giving a cherry red colored solution. The SizCu ratio found by microanalysis was 2.17 :1 as compared to a theoretical value of 2.00:1.

The above siloxane azo dyestufis were used to dye various fibers from a methanol-pyridine dyebath solution.

, Color Source Fiber dyed Example 1 Example 2 Cotton Rust-brown,.H Orange-brown, H. Wool Rose, M Orange-brown, M. Silk Rose, L Orange-brown, M. Nylon ,Rose, M Orange, L. Viscose Rose, L. Orange-brown, L. Acetate- Orange, M Orange. H. Glass Rose, VL Orange-brown, VL-

VL=very light shade. L=light shade. M-medium shade. H==heavy shade.

The dyeings could also be performed from an aqueous bath at the boil.

" Example 3 There was added 0.1 g. of the siloxane azo dyestufi produced in Example 1 to a mixture of 0.2 g. of sodium carbonate, 3 g. of water and 3 g. of glycerine. The mixture was stirred at room temperature for about 15 minutes, and a red solution was obtained. This solution wasfiltered, and the filtrate was used to write on paper. After standing in water at room temperature for two days, the ink was removed.

What is claimed is: V

l. Polysiloxane azo dyestuffs containing units represented by the general-formula:

wherein R represents the residue of an aromatic coupling component; Ar represents an arylene radical selected,

from the group consisting of a phenylene radical, an alkyl substituted phenylene radical and an alkoxy substituted phenylene radical; Y represents a member selected from the group consisting of alkyl radicals; a is an integer having a value of from O to about 8; and b is an integer having a value of from. 0 to 2.

2. Polysiloxane azo dyestufis containing the unit represented by the general formula:

wherein R represents the residue of an aromatic coupling component; Ar represents an arylene radical selected from the group consisting of a phenylene radical, an alkyl from the group consisting of a phenylene radical, an j alkyl substituted phenylene radical and .an alkoxy substituted phenylene radical; Y represents a member selected from the group consisting of alkyl radicalst a is an integer having a value of from 0 to about 8.

5. The polysiloxane azo dyestutf containing units represented in the free acid form by the formula:

8. The disiloxane azo dyestufi represented by the Qomomsiom 6. The metallized polysiloxane azo dyestuff containing units represented by the formula:

on C -on,on,s10m i in Cu 7. The polysiloxane azo dyestufi containing units represented by the formula: v

=N-O-omomsiio formula:

N=NO i0u| 9. The method of dyeing fibrous material, which comprisesexposing said fibrous material to a dye bath containing a siloxane azo dyestufi containing units represented by the general formula:

wherein R represents the residue of an aromatic coupling component; Ar represents ,an arylene radical selected from the group consisting of alkyl radicals; a is an alkyl substituted phenylene radical and an alkoxy substituted phenylene radical; Y represents amember selected from the group consisting of alkyl radicals; a is an integer having a value of from 0 to about 8; and b is an integer having a value of from 0 to 2, at an elevated temperature, rinsing, and drying.

4. Polysiloxane azo dyestufis represented by the general formula:

R-N=NAt-CHz,,i0m wherein R represents the residue of an aromatic coupling component; Ar represents an arylene radical selected a 10. A fiber dyed with a siloxane azo dyestufi of claim 1. 11. Glass fiber dyed with a siloxane azo dyestufi of claim 1. r v

12. Silica dyed with the polysiloxane azo dyestuffs of claim 1.

7 References Cited in the file of this patent V UNITED STATES PATENTS 2,029,568 Iaeck Feb. 4, 1936 2,317,965 Bestian Apr. 27, 1943 2,715,133 Speier Aug. 9, I955 2,778,746 Steinman Ian. 22, 1957 2,832,754 Jex Apr. 29, 1958 2,849,333

Kingsbury Aug.'26, 1958- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2327 839 March B 1960 Donald L, Bailey et'alo It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should readas corrected below.

Column 6, line 52 for alkyl radicals; a is read a phenylene radical,

Signed and sealed this 6th day of September 1960.

(SEAL) Attest: ERNEST W, SWIDER ROBERT C. WATSON Attesting Officer 1 Commissioner of Patents 

9. THE METHOD OF DYEING FIBROUS MATERIAL, WHICH COMPRISES EXPOSING SAID FIBROUS MATERIAL TO A DYE BATH CONTAINING A SILOXANE AZO DYESTUFF CONTAINING UNITS REPRESENTED BY THE GENERAL FORMULA: 